Modified aminoplast compositions and products



Patented Jan. 15, 1952 luomrmn AMINOPLAST ooMrosrrIoNs AND rnonvors Henry P. Wohnsiedler, Darien, and Edward L. Kropa, Old Greenwich, Conn., assignors to American Cyanamid Company, New York, N. Y., v a corporation of Maine No Drawing. Application November 25, 1950, Serial No. 197,641

18 Claims. (01. 154-43) This invention relates to new and useful compositions having properties that render them particularly useful in the plastics, coating, laminating and other arts, and to products prepared therefrom. More particularly, the invention is concerned with compositions of matter comprising 1) a product of reaction of ingredients comprising (a) an aldehyde, e. g., formaldehyde, furfural,v etc., and (b) a monomeric amidogen compound containing not less than two amidogen groupings, each having at leastone hydrogen atom attached to the amidogen nitrogen atom, and (2) at least one substance of the class consisting of polyethylene melamines (e. g., diethylene melamine, triethylene melamine and mixtures thereof), alcohol-reaction products of a. polyethylene melamine and amine-reaction products of a polyethylene melamine. The ingredients of (1) and (2) may be used in various proportions but advantageously are employed in a weight ratio of 25 to 97% of the former to from 3 to 75% of the latter. Preferably the ingredient of (2) constitutes at least about 5% and not more than about 50 or 60% by weight of the total of (1) and (2).

From the preceding paragraph it will be seen that the present invention is concemed with compositions of matter and products comprising a modified aminoplast, specifically a modified,

heat-curable (thermosetting) or a heat-cured (thermoset) resinous or other product of reaction of the ingredients described under (a) and A (b) above, which aminoplast has been modified with a polyethylene melamine, or with an alcoholor an amine-reaction product of a polyethylene melamine, or with a. mixture of two "or more such substances. The scopeof the invention also includes products prepared from such compositions, e. g., molded articles of any dee sired shape or size, as well as laminated articles comprising superimposed sheets of fibrous material impregnated and bonded together with a modified aminoplast of the kind briefly described above.

As is well known, aminoplasts are synthetic resins derived from amino (including imino) erably two hydrogen atoms) attached to the I amidogen nitrogen atom. Amidogen compound, as used herein, has reference to an amino or an amido compound, and more particularly to such a compound (unless stated otherwise) which contains not less than two amidogen (amino or amido) groupings, each having at least one hydrogen atom attached to the amidogen nitrogen atom. Urea and melamine are typical examples of amidogen compounds.

In the commercial utilization of aminoplasts in the plastics, coating and laminating arts,-it is frequently necessary to modify the heat-curable (heat-convertible) or potentially heat-curable aminoplast by incorporating therein a modifying agent which will improve the useful properties of the aminoplast. In some cases this modifier is a plasticizer or softener which will so improve the aminoplast that it will flow properly in the particular coating or laminating composition or, in the case of thermosetting aminoplast molding compositions, will show good plastic flow characteristics during molding. For example, if improper or insufiicient plastic fiow occurs during the molding operation, the molded articles may show streaked or wavy surfaces. Furthermore, if the plasticityof the molding composition is not suflicient, lack of physical homogeneity as the result of incompletely knitted granules often characterizes the moldings, especially massive moldings. In other instances, the modifier is a substance which will toughen molded articles produced from the modified aminoplast, whereby molded pieces are obtained which show better strength characteristics than those produced from unmodified aminoplasts.

In filled (e. g., cellulose-filled) molding compositions, it is also important that any plasticizer employed be compatible with both the cellulose and the aminoplast, e. g., a melamineformaldehyde resin, so as to obtain molded articles having optimum dimensionalstability and resistance to cracking around inserts. With both unfilled and filled aminoplast compositions, it is also desirable that the molded piece show minimum shrinkage of the initially molded article with respect to the cold dimension of the mold, which shrinkage is commonly referred to as cold mold to cold piece shrinkage. Another desirable property of both unfilled and filled aminoplast compositions is that they show minimum shrinkage on aging.

In impregnating, coating and laminating compositions wherein the aminoplast is utilized in the form of a solution thereof, it is also important that the modifier (e. g., a plasticizer, a

toughening agent, etc.) for the aminoplast be to withstand sudden shocks and strains.

soluble in the same solvent in which the aminoplast is dissolved, and for economic reasons it is also desirable that this solvent be relatively inexpensive.

In the production of, for example, laminated structures, e. g., paperand canvas-filled laminates, it is also important that the aminoplast binder impart optimum fiexural-strength characteristics to the laminate, and that it be possible to subject the laminated article to sawing, punching, drilling and other fabrication operations without cracking, chipping, breaking or other damage thereto. These properties and, in some cases, workability are also desirable in molded aminoplast articles wherein the filler is of the finely divided type, i. e., finely divided alphacellulose. It is apparent, therefore, that in many instances it is desirable that the modifier of the aminoplast be able to toughen the cured aminoplast so that it will be able efiectively In numerous cases such a toughening agent advantageously is one which also imparts plasticizing or softening action to the heat-curable aminoplast as it assumes its ultimate form or shape. Generally, plasticizers and toughening agents perform several functions in a molding composition. The lower-molecular-weight substances generally promote fiow and increase the plasticity of the product whereas the highermolecular-weight components act as toughening agents.

From the foregoing, it will be seen that in the utilization of modified aminoplasts (e. g., modified resinous reaction products of formaldehyde or other aldehyde with urea, thiourea,

iminourea (guanidine), dicyandiamide, guanylurea, biguanide, melamine, guanylmelamine, mixtures thereof in any proportions, etc.), in molding, impregnating, coating, laminating, casting and other applications, it is important that the modifier,- e. g., a plasticiser and/or toughening agent, have certain characteristics. The particular characteristics or combination of characteristics desired in the modifier obviously will vary to some extent depending upon the particular service application of the modified aminoplast. Some of these characteristics, more particularly the necessary requisites of a plasticiser for an aminoplast, are described more fully in the copending application of Henry P. Wohnsiedler, Edward L. Kropa, and Walter M. Thomas, Serial No. 21,856, filed April 19, 1948.

The present invention is based on our discovery that polyethylene melamines (diethylene melamine, triethylene melamine or a mixture of diand triethylene melamines in any proportions), as well as certain reaction products thereof (e. g., alcoholand amine-reaction products of a polyethylene melamine), constitute a class of materials that are particularly adapted for use as modifiers of aminoplasts obtained by reaction of ingredients comprising an aldehyde, e. g., formaldehyde, and a monomeric amid'ogen compound containing not less than two amidogen groupings each having at least one hydrogen atom (preferably two hydrogen atoms) attached to the amidogen nitrogen atom. More particularly, we have discovered that such modifiers have the peculiar and distinctive property of reducing the shrinkage (especially the after- -shrinkage) of molded articles produced irom aminoplasts into which'such modifiers have been incorporated. This was quite unexpected and unpredictable. We are unable to explain with certainty why polyethylene melamines and certain reaction products thereof have this unusual property when incorporated into an aminoplast composition, but a possible explanation is the following:

Polyethylene melamines theoretically are capable of combining with water, and it is because of this theoretical possibility that the improvement in shrinkage characteristics may be due. Since the after-shrinkage" or aging-shrinkage of molded articles produced from aminoplast molding compounds is directly traceable to the confined moisture and its gradual difiusion out of the structure, it is quite likely that polyethylene melamines and certain reaction products thereof function to fix this free moisture through chemical combination and thereby serve to control or limit the shrinkage of the molded article both initially and upon aging, e. g., either at normal temperature or at an elevated temperature.

It is quite likely that the modifiers used in practicing the present invention co-react with the amidogen-aldehyde aminoplast, with the result that the modified aminoplasts are difierent in kind (as evidenced by their differences in properties, from the modifier and the amidogenaldehyde aminoplast which are combined to produce the new compositions and products of the present invention.

Triethylene melamine is a known compound and can be prepared, for example, by the method described in Wystrach and Kaiser Patent No. 2,520,619. The formula for triethylene melamine 85 is while the formula for diethylene melamine is Diethylene melamine can be prepared, -for instance, as described in the copending application of Frederic Schafer, Serial No. 165,861, filed June 2, 1950. These polyethylene melamines may be described as being s-triazine (1,3,5-triazine) derivatives wherein at least two of the amino nitrogen atoms of a polyamino-s-triazine each has one ethylene group attached thereto inno stead of the two hydrogen atoms.

In our copending application Serial No. 197,637, filed concurrently herewith, we have disclosed and claimed compositions comprising the product of reaction of ingredients comprising 1) a polyethylene melamine and (2) a different nitrogenous compound containing a radical represented by the formula where R represents a member of the class consisting of hydrogen and hydroxyhydrocarbon radicals and R represents a member of the class consisting of hydrogen, hydrocarbon radicals and hydroxy- 7 hydrocarbon radicals. Such reaction products dients comprising either diethylene melaminev triethylene melamine or a mixture of diethylene melamine and triethylene melamine in any proportions with butyl amine, amyl amine, octyl amine, 1,4-diaminobutane, diethylene triamine, tetraethylene pentamine, ethanolamine, diethanolamine. triethanolamine. aniline. 4-amino-2- ,butanol, l-methylamino-Z-propanol or any of the other compounds containing a radical represented by the aforementioned general formula that are given by way of illustration in our aforesaid copending application Serial No. 197,637.

To the best of our knowledge and belief, any monohydric or polyhydric alcohol can be used as a reactant with a polyethylene melamine (or mixture of polyethylene melamines) to form a reaction product that can be used as a modifier in producing the modified aminoplasts of the present invention. Numerous examples of such reaction products are given in our copending application Serial No. 197,638, also filed concurrently herewith. In that application we have disclosed and claimed compositions comprising the product of reaction of ingredients comprising (1) a polyethylene melamine and (2) a non-nitrogenous hydroxy compound which contains carbon having bonded directly thereto at least one and not more than six hydroxy groups per molecule, for instance methanol, ethanol, propanol, the glycols (e. g., ethylene glycol, diethylene glycol, triethylene glycol, etc.), glycerol, pentaerythritol, sorbitol, mannitol, ethylene glycol monoethyl ether, phenol, resorcinol, etc., or mixtures thereof, e. g., a mixture of amonohydric alcohol and a polyhydric alcohol containing not more than six alcoholic hydroxyl groups, a mixture of a phenol (e. g., phenol itself, mor p-cresol or mixtures thereof, a xylenol, an ethylphenol, etc.) and a monohydric alcohol and/or a polyhydric alcohol containing not more than six alcoholic hydroxyl groups, as well as other mixtures of hydroxy compounds of the kind aformentioned.

Reaction products of the kind disclosed in our aforesaid application Serial No. 197,638, as well as others, can be used as modifiers in producing the modified aminoplasts of the present invention. It is to be distinctly understood, however, that in carrying the instant invention into effect we are not limited only to the use of reaction products of a polyethylene melamine and an alcohol containing not more than six alcoholic hydroxyl groups, since we can use such reaction products made from alcohols containing any number of alcoholic hydroxyl groups, e. g., seven, eight, nine, ten, twelve, fifteen, twenty or any higher number, including polyvinyl alcohol, polyallyl al'coholcontaining an average of, for instance, from four to twelve or more alcoholic hydroxyl groups, etc.

Illustrative examples of amidogen-aldeyde aminoplasts which can be modified with a polyethylene melamine, or with an alcoholor an amine-reaction product of a polyethylene melamine, or with a mixture of any two or of all of such substances, are "aminotriazine-aldehyde resins (e. g., melamine-formaldehyde resins), urea-aldehyde resins (e. g., urea-formaldehyde 'resins), thiourea-aldehyde resins (e. g., thiourea-aldehyde resins (e. g;, thiourea-formaldehyde resins), urea-aminotriazine-aldehyde resins (e. g., urea-melamine-formaldehyde resins),

aminodiazine-aldehyde resins (e. g., aminodiazine formaldehyde resins), protein-aldehyde resins (e. g., casein-formaldehyde resins), resinous condensation products of an aldehyde, e. g., formaldehyde, with a polyamide of a polycarboxylic acid, e. g., malonic diamide, succinic diamide, fumaric diamide, itaconic diamide, phthalic diamide, citric triamide, etc.

The amount of the modifier of the kind used in practicing the present invention and which is incorporated into the amidogen-aldehyde aminoplast to obtain a modified aminoplast composition having improved useful properties, e. g., improved shrinkage resistance, may be widely varied as desired or as conditions may require. In some cases, only a relatively small amount may be required, e. g., about 3 or 4% by weight of the combined amount of modifier and aminoplast. Ordinarily, however, the modifier constitutes, by weight, from about 5% to about and more specifically from about 5%- to about ,50 or 60%, of the combined amount of modifier and aminoplast. Thus, depending upon the particular service application of the modified aminoplast, the

. modifier may constitute from 5-l0% to 30-40% by weight of the combined weight of modifier and aminoplast.

Any suitable means can be employed for incorporating the modifier into the amidogen-aldehyde aminoplast. For example, a modified aminoplast can be preparedjoyfirst mixing together the amidogen compound, aldehyde and modifier used in practicing the present invention (e.- g..

diethylene melamine, triethylene melamine, or a mixture thereof; or an alcoholor an aminereaction product of dlethylene melamine, tri'ethylene melamine or a mixture thereof; or a mixture of any two or all of such modifiers). There.- after simultaneous reaction is effected between the reactive ingredients of the mixture in the persed in a suitable liquid medium, if des'irect' during the reaction.

Alternatively, the, modifier used in practicing our invention can be incorporated, if desired, into the heat-curable amidogen-aldehyde aminoplast at any suitablestage of the manufacture of a molding, coating, impregnating, laminating or other composition therefrom. For example, the

modifier may be dryor wet-blended with the amidogen-aldehyde resin (e. a melamine formaldehyde resin, etc.), a filler'(e. g., alphacellulose, wood flour, etc.), a mold lubricant (e. a. zinc stearate, etc.), and, if desired, acuring catalyst (e. g., phthalic anhydride, tetrachlorophthalic anhydride, ammonium chloride, oxalic acid, acetic acid, phosphoric acid, diammonium phthalate, diammonium hydrogen phosphate, diammoa nium ethyl phosphate, ammonium silicofiuoride, a melamine fiuosilicate, a melamine fiuoborate,

melamine pyrophosphate, chloroacetamide, su:

cinic acid, etc.) Thereafter the mixture is worked on hot rolls to cause the modifier to become homogeneously incorporated (as by chemical combination) with the amidogen-aldehyde aminoplast hyde aminoplast and the modifier in a suitable mutual solvent. For example. in the case of water-soluble, alcohol-soluble or waterand alcohol-soluble urea-formaldehyde, melamine-formaldehyde, urea-melamine-formaldehyde resins, and the like, the liquid composition can be prepared merely by admixing with such a solution a modifier (or modifiers) oi the kind used in practicing the present invention and which .also is soluble in the same solvent or mixture .of solvents, or which can be made soluble therein by the addition of another solvent.

In order that those skilled in the art better may s am understand how the present invention can be carried into efiect, the following examples are given by way of illustration and not by way of limitation. All parts and percentages are by weight.

' EXAMPLE 1 Parts Melamine-formaldehyde resin 190.0 Triethylene melamine 10 0 Zinc stearate 0.4

N0TI:.--Resinous reaction product of melamine and formaldehyde in a molar ratio of approximately 2 moles of HCHO per mole of melamine. This resin advantageously can be prepared by the process disclosed in Wohnsledler and Thomas copending application Serial No. 675.296, filed June 7, 1946, now Patent No. 2,563.630

dated August 7, 1951. The cure of the resin was advanced by heating in a 110 C. oven for 2% hours prior to passage through an Abbe cutter provided with a lit-inch screen, followed by further drying at from 70 to 150 C. prior to use in the above formulation.

The above ingredients were ball-milled together for about hours, screened through a 60- mesh screen and then stored in a closed container until portions thereof were molded. A

well-molded disc, 3 inches in diameter, was produced by molding a sample of the composition for 20 minutes at 155 C. under a pressure of 3000 pounds per square inch. The molded disc had a good surface appearance and showed good plastic flow during molding.

A control sample produced by similarly ballmilling a mixture of 200 parts of the same melamine-formaldehyde resin and 0.4 part of zinc stearate was molded in exactly the same manner as the melamine-formaldehyde resin which had been modified with triethylene melamine. The

shrinkage data on the unmodified and modified melamine-formaldehyde resins are shown below;

1 Shrinka e on Aging at gg gg 220 F. for

Piece I shrinkage 2 days 1 week 2 weeks I Unmodified resin 7. 9 4. 6 8. 6 l1, 9 Modified resin 7.7 3.4 5.9 l 8.4

respect to the cold dimension of the mold.

8 Additional shrinkage of the molded piece alter aging by heating at 220 F. (or the specified periods.

Parts Melamine-formaldehyde resin 270.0 Triethylene melamine 30.0 Zinc stearate 0.6 Magnesium oxide 0.3

The melamine-formaldehyde resin used in this example was the same as that employed in Example 1. A molding composition was prepared from a mixture of the above ingredients likewise as described in Example 1. A s mple" of the molding compound was molded in the form of a disc, 3 inches in diameter, by m dingfor 30 minutes at 155 C. under a pressure I 3,000 lbs. per square inch. A control sample (same as the other sample with the exception that .it contained no triethylene melamine) was prepared and molded in a similar manner with th'emxception that the time of molding was 20 utes instead of 30 minutes The shrinkage-da on the unmodified and modified melamine-formaldehyde resins are shown below:

I Shrinkage on ikging at Gold Mold toold Piece shflPkm 2days llweek 2weeks Unmodified resin 1.9 5.0 9; s 12. 5 Modifiedresin 1.1 3.1 as .4

EXALJPLE 3 This example illustrates the modification of a cellulose-filled melamine-formaldehyde resin with triethylene melamine.

Parts Cellulose-filled melamine-formaldehyde resin 750.0

Triethylene melamine 18.7 Phthalic anhydride 0.41 Zinc stearate 8.25

Nora,'.lhis fllied resin contained approximately 35 parts of alpha-cellulose and parts of a resinous reaction product of formaldehyde and melamine in the ratio of ilzpgroximately 3 moles of the former to 1 mole of the a er.

All of the above ingredients with the exception of 3.3 parts of zinc stearate were ball-milled together for a total of 18 hours, the remainder (3.3 parts) of zinc stearate being added one hour before the end of the grinding period, and ball-milling then was continued to form a homogeneous composition.

Another composition was prepared in exactly the same manner described under A of this example with the exception that there was used 37.5 parts of triethylene melamine instead of 18.7 parts.

A control sample was prepared in exactly the same manner described above with reference to the compositions of A and B except that no triethylene melamine was incorporated in the composition. Samples A, B and C were molded in the ores: Shrinkage in mills per inch of the initially molded piece with same manner described under Example 1. The molded pieces had a good appearance, the molded article produced from the B composition being a somewhat deeper yellow than that of A composition. The shrinkage data on aging the un- 76 modified and triethylene melamine-modified Shrinkage on aging at 220 F. for 2 days Unmodified composition of C 4.5 Modified composition of A 3.33 Modifi ed composition of B 2.2 I

' EXAMPLE 4 A melamine-formaldehyde resin produced in essentially the same manner described under Example 1 (142.5 parts) and 0.4 part of zinc stearate were ground together in a ball-mill for approximately 16 hours, after which the ground composition was dried in an oven at 65 C. for 1 hour prior to use as a molding compound.

Parts Same melamine-formaldehyde resin as was used in A 142.5 Reaction product of triethylene melamine and methyl alcohol 1 NoTE.The triethylene melamine-methyl alcohol reaction product was prepared by heating together 100 parts of triethylene melamine and 317 parts methyl alcohol under reflux at a temperature of 6768 C. for 2 hours and 33 minutes. The resulting composition contained about 30% of solid reaction product.

The above ingredients were mixed together until a uniform blend had been obtained, after which the mixture was allowed to stand in the air until dry. The air-dried blend (167.5 parts) and 0.5 part of zinc stearate were ground together in a ball-mill for approximately 16 hours, after which the ground material was dried in an oven at 65 C. for 1 hour prior to use as a molding composition.

Exactly the same procedure was followed as described under B with the exception that the blend was formed of 135.0 parts of the melamineformaldehyde resin and 50.1 parts of the triethylene melamine-methyl alcohol reaction product. The air-dried blend (185.1 parts) was ground with 0.5 part of zinc stearate in the same manner described under B, and thereafter oven-dried also in the same manner as was set forth under B.

Samples of A, B and C were molded into the form of 3-inch discs in essentially the same manner described in Example 1. The control sample (A) showed a cold mold to cold piece shrinkage of 8.3 mils per inch whereas the corresponding values for the molded pieces of B and C were 7.7 and 7.2 mils, respectively. When each of the molded pieces was heated for 48 hours at 220 F. the molded control sample cracked badly whereas no cracking whatsoever was noted on either of the molded pieces of B or C.

EXAMPLE 5 The formulation and procedure are exactly the same as described under Example 1 with the exception that parts of diethylene melamine instead of 10 parts of triethylene melamine are used. Improvements in cold mold to cold piece shrinkage and in shrinkage on aging similar to those described under Example 1 are obtained on molded pieces of the diethylene melamine-modifled melamine-formaldehyde resin as compared with the unmodified resin.

EXAMPLE 6 Same as in Example 1 with the exception that 100 parts of a urea-formaldehyde, resin produced by reactionof about 1.5 moles of formaldehyde per mole of urea are used in place of 190 parts of melamine-formaldehyde resin. Similarresults areobtained.

. v p Parts Melamine-formaldehyde resin 90.0 Triethylene melamine-methyl alcohol re-' action product (same aswas used in Ex-' I ample 4) 33.4 Zine steara 0.9 Magnesium oxide 0.45

Nora-Produced by reaction ofgformaldehyde and melamine in the ratio of approximately 2 moles of the former to 1 mole of the latter, and advancing the cure by working on hot rolls. i g Y The above ingredients were mixed together without any evidence of stickiness, after which the mixture was transferred to a tray and airdried prior to ball-milling for about 16 hours.

The ground blend was then oven-dried for about one hour at 65 C.

Samples of the molding composition produced as above described were molded under heatand v pressure in the same manner as described under Example 1, aswere also samples of ,a molding composition which had been prepared in-a similar manner with the exception that theireaction product of triethylene melamine and methyl alcohol was omitted from the formulation. Both the unmodified and modified melamine-formaldehyde molding compositions yielded well-"curedof the molded article produced'from the modified melamine-formaldehyde resin was only 4.8 mils approximately 50% of resin solids" c I 1 A reaction product of ingredientse'omprising triethylene melamine and n-butyl amine was prepared as follows: 1

were mixed together to yield a solutioncontaining 0' v Parts Triethylene melamine". .L c;.. 75.0 n-Butyl amine 26.8

Ethyl alcohol f 302.5

The above ingredients were heated together to an initial reflux temperature of 77C. over a period of '7 minutes, and then under vigorous reflux at 81 C. for an additional 36 minutes.

After only 23 minutes of vigorous refluxing, a

sample taken from the reaction mass'wasi-clear when cool. The, reaction product wasm'ixed with a small amount of diatomaceous earth,- pressu'refiltered and the clarified liquid then. usedasa modifier of the solutionoffA. p v

' Parts Solution of A--- 75 Reaction product of B 75 were thoroughly mixed together to form a laminating composition. Laminated articles were prepared by impregnating sheets of paper by immersion in this composition, drying the impregnated sheets horizontally on a frame in a drier, superimposing 8 sheets of the dried. impregnated paper, and then laminating the assembled sheets by compressing for 30 minutes at 155 C. under a pressure of about 1000 pounds per square inch. In one case the sheets of wet, impregnated paper were dried for 15 minutes at 50 C.. yielding dried sheets containing approximately 37% by weight of resin. In another case the wet, initially impregnated sheets were dried for 15 minutes at 50 C., immersed again in the laminating composition. and re-dried for 30 minutes at 50 C. The dried sheets contained about 44% by weight of resin. In both instances strong, translucent, well-bonded laminated articles having lair flexibility were obtained.

Similar results are obtained when the reaction product of B is one produced by reaction of 75.0 parts of triethylene melamine and 26.8 parts of n-butyl amine in the absence of the ethyl alcohol, and, at the end oi! the reaction period, adding 302.5 parts of ethyl alcohol to the triethylene melamine-n-butyl amine reaction product.

EXAMPLE 9 Parts Solution A of Example 8 120 Reaction product or B of Example 8 240 1 Water 209 EXAMPLE 10 Parts Melamine-formaldehyde resinisame as in A of Example 8) 250 Water 125 Ethyl alcohol 125 were mixed together to yield a solution containing approximately 50% of resin solids.

A reaction product of ingredients comprising triethylene melamine and ethanolamine (monoethanolamine) was prepared as follows:

Ap rox.

Parts olar 7 Ratio 'lriethylene melamine 90 1 Ethanolamine 27 l Ethanol (ethyl alcohol).. 217

were heated together, with stirring, in a reaction vessel fitted with a reflux condenser and placed in an oil bath. The temperature of the mass was brought to 66 C. in minutes. After heating to 74 C. in an additional minute, the solids had completely dissolved. Refluxing began a minute later at 81 C., and was caused'to continue for a total of 8 minutes. The solution comprising the reaction product was cooled to 28 6.. a small amount of insoluble matter being present in the cooled solution. A sample or the solution was dried to yield a clear, balsam-like material, which became a fairly hard resin after drying for about 16 hours. Filtration of the bulk or the liquid product gave a clear, water-white solution which tolerated 5 parts of water per 1 part 01' the solution without clouding.

I I Parts Solution of A 240 Reaction product of 3---- 171 were thoroughly mixed together to form a laminating composition. Sheets 01' paper were twice immersed in this composition, being dried for 30 minutes at 50 C. after each immersion. The flnal, dried sheets contained about 59% by weight of resin. Fourteen (14) sheets of the dried, impregnated paper were assembled and laminated together as described under Example 9. A strong, translucent, well-bonded laminated article was obtained.

EXAMPLE 1i Same as in A of Example 10.

A reaction product of ingredients comprising triethylene melamine and pentaerythritol was prepared as follows:

Ap mx. Parts ltolr Ratio Triethyiene melamine 2 Pentacry thritol. 30 l Ethyl alcohol 360 26 0.5 N aqueous sodium hydroxide solution (catalyst) l2 A mixture of the above ingredients was heated with stirring in a reaction vessel provided with a stirrer and a reflux condenser, being brought to reflux temperature (80-82 C.) in 17 minutes and thereafter vigorously refluxed for 1 hour and 33 minutes. The solution comprising the reaction product was pressure-filtered to yield a clear solution.

, Parts Solution of A Reaction product of B 125 EXAMPLE 12 This example illustrates the modification of a cellulose-filled urea-formaldehyde resin with triethylene melamine.

- Parts Cellulose-filled urea-formaldehyde resin --'150.0 Triethylene melamine 18.7 Phthalic anhydride 1.16 Zinc steal-ate 3.75

lo'rI!:.-This filled resin contained approximate parts of alpha-cellulose and parts of a resinous reac on product of formaldehyde and urea. in the ratio of approximately 1.5 moles of the former to 1 mole of the latter.

All of the above ingredients with the exception of 1.5 parts of zinc stearate were ball-milled together for a total of 18 hours, the remainder (1.5 parts) of zinc stearate being added one hour before the end of the grinding period, and ballmilling then was continued to form a' homogeneous composition.

Another composition was prepared in exactly the same manner described under A of this example with the exception that there was used 37.5 parts of triethylene melamine instead of 18.7 parts.

A control sample was prepared in exactly the same manner described above with reference to the compositions of A and B with the exception that no triethylene melamine was incorporated in the composition. Samples of A, B and C were molded in the same manner described under Example 1. The molded pieces had a good appearance, the molded articles produced from the A and B compositions having a lower after-shrinkage (shrinkage on aging at 220 F. for 2 days and longer) than the control sample.

It will be understood, of course, by those skilled in the art that our invention is not limited to the specific compositions or to the particular procedures given in the above illustrative examples. Thus, instead of the particular modifiers employed in the examples we can use, depending, for instance, upon the particular amidogen-aldehyde reaction product which is being modified and the particular use intended for the modified product, any other polyethylene melamine (or 14 thiourea-melamine-formaldehyde resinous reaction products also can be employed. Dimethylol 'urea, alkyl ethers thereof, polymethylol melamines (more particularly mono-, di-, tri-, tetra-, pentaand hexamethylol melamines) and alkyl ethers thereof can be used. Examples of other amidogen compounds that can be reacted with an aldehyde to provide the primary reaction product which is modified in accordance, with the present invention are: methylurea, phenvlurea. phenylthiourea, allylurea, guanylurea, guanylthiourea, dicyandiamide, guanidine, biguanide. diaminodiazines, guanazole and other diaminotriazoles, ammeline, ethylenediamine, etc. Any suitable aldehyde can be employed as a reactant with the amidogen compound in forming the aminoplast. We prefer to use formaldehyde, e. g., aqueous solutions of formaldehyde. Paraformah dehyde, hexamethylene tetramine, or othencompounds engendering formaldehyde also can be used. In certain cases other aldehydes, e. g., acetaldehyde, propionaldehyde, butyraldehyde, furfural, acrolein, methacrolein, crotonaldehyde, octaldehyde, ben'zaldehyde, mixtures thereof, or mixtures of formaldehyde (or compounds engendering formaldehyde) with such other aldehyde or aldehydes, can be employed. The choice mixture of polyethylene melamines) or any other reaction product of' ingredients comprising an amine or an alcohol, or both an amine and an alcohol, and diethylenemelamine, triethylene melamine or a mixture thereof in any propor tions, or a mixture in any proportions of a polyethylene melamine and an amineand/or an alcohol-reaction product of a polyethylene melamine, numerous examples of which modifiers have been given hereinbefore and in our aforementioned copending applications.

Our invention is operative with reaction products of an aldehyde, specifically formaldehyde, and any monomeric amidogen compound containing at least two aldehyde-reactable amino or amido or amino and amido groupings, that is to say, any monomeric amidogen compound containing at least two amidogen groupings, each having at least one hydrogen atom (preferably two hydrogen atoms) attached to the amidogen nitrogen atom.

As amidogen-aldehyde aminoplasts we prefer' of the aldehyde is dependent upon such factors as, for instance, the particular properties desired in the finished product and economic considerations.

The amidogen-aldehyde aminoplasts are prepared, in general, in accordance with technique well known to the art. The molar ratio of aldehyde to amidogen compound, depending, for instance, upon the particular amidogen compound employed, may vary, for example, from 0.35 mole to 2.0 moles thereof for each aldehyde-reactable amidogen grouping in the amidogen compound.

Dyes, pigments and opaciflers may be incorporated into the compositions of this invention to alter the visual appearance and the optical properties of the finished product. If needed, mold lubricants may be added to facilitate molding of the heat-convertible (heat-hardenable) molding compositions. Fillers (e. g., alpha-cellulose, asbestos, mica, wood flour, etc.) may be incorporated to obtain a wide variety of molding compounds and molded articles .adapted to meet particular conditions. Curing agents, examples of which have been given hereinbefore, also can be added. Other efiect agents also may be incorporated as desired or as conditions may require.

Thermosetting (heat-hardenable) molding compositions comprising a heat-curable or potentially heat-curable amidogen-aldehyde aminoplast which has been modified, specifically plasticized and/or toughened and/or rendered shrinkage resistant either initially after withdrawal from the mold or after further aging, as herein described, can be molded into a variety of shapes under heat and pressure, more particularly at temperatures of the order of to 200 0., preferably from approximately or to or C.

The modified amidogen-aldehyde aminoplasts of our invention are especially suitable for use in producing molded and laminated articles, for example, laminates comprising superimposed sheets of fibrous material such as paper, glass cloth, or cloth formed of silk, wool, cotton, rayons, etc., or cloths produced from synthetic fibers, e. g., fibers of nylon, polyacrylonitrile (or copolymers of acrylonitrile), vinyl chloride-acrylonitrile copolymers, vinyl chloride-vinylidene aseavso 15 chloride copolymers, etc. In such structures the sheets are impregnated and bonded together with a thermoset product of reaction of ingredients comprising an aldehyde, specifically formaldehyde, and a monomeric amidogen compound of the kind aforementioned, which reaction product is modified with a modifier of the kind previously described.

Our modified amidogen-aldehyde aminoplasts are also useful in the treatment of paper or for incorporation therein during its formation, e. g., by addition to the beater prior to formation, in order to make a wet-strength paper. They are also useful as adhesives, as components of surface-protective compositions and for numerous other purposes. In the filled compositions the amount of filler (examples of which previously have been given) may be widely varied depending, for example, upon the particular filler em'- ployed and the intended use of the filled composition. Thus, the amount of filler may constitute, for instance, from a few per cent (e. g., from 2 to or up to 50 or 60%, or even as much as 70 or 80% in some cases, by weight of the combined weight of filler and modified amidogenaldehyde aminoplast.

We claim:

. 1. A composition of matter comprising (1) a product of reaction of ingredients comprisinga) an aldehyde and (b) a monomeric amidogen compound containing not less than two amidogen groupings each havin at least one hydrogen atom attached to the amidogen nitrogen atom, and (2) at least one substance of the class consisting of polyethylene melamines, alcohol-reaction products of a polyethylene melamine and amine-reaction products of a polyethylene melamine, the ingredients of (1) and (2) being employed in a weight ratio of from to 97 per cent of the former to from 3 to 75 per cent of the latter, and the aforementioned polyethylene melamine being a polyamino-s-triazine wherein at least two of the amino nitrogen atoms each has one ethylene group attached thereto instead of the two hydrogen atoms.

2. A composition as in claim 1 wherein the aldehyde of (a) is formaldehyde.

3. A composition as in claim 1 wherein amidogen compound of 4b) is urea.

4. A composition as in claim 1 wherein amidogen compound of (b) is melamine.

5. A composition as in claim 1 wherein the substance of (2) is triethylene melamine. the formula for which is.

the

6. A composition as in claim 1 wherein the substance of (2) is a reaction product of a monohydric alcohol and triethylene melamine, th formula for which is.

the

7. A composition as in claim 6 wherein the monohydric alcohol is methyl alcohol.

8. A composition as in claim 1 wherein the substance of (2) is a reaction product of a hydrocarbon amine and triethylene melamine, the formula for which is.

9. A composition as in claim 8 wherein the hydrocarbon amine is n-butyl amine.

10. A composition as in claim 1 wherein the substance of (2) is a reaction product of an alkanolamine and triethylene melamine, the formula for which is.

112C N N CH:

11. A composition as in claim 10 wherein the alkanolainine is monoethanolamine.

l2. Aheat-curable composition comprising (1. a heat-convertible product of reaction of ingredients comprising (a) formaldehyde and (b) a monomeric amidogen compound containing not less than two amidogen groupings each having two hydrogen atoms attached to the amidogen nitrogen atom and (2) at least one substance of the class consisting of polyethylene melamines, alcohol-reaction products of a polyethylene melamine. and amine-reaction products of a polyethylene melamine, the ingredients of (1). and (2) being employed in a weight ratio of from 25 to 97 per cent of the former to from 3 to-75 per cent of the latter, and the aforementioned polyethylene melamine being a polyaminos-triazine wherein at least two of the amino nitrogen atoms each has one ethylene group attached thereto instead of the two hydrogen atoms.

13. A product comprising the cured composition of claim 12.

14. A composition as in claim 12 wherein the amidogen compound of (b) is melamine.

15. A heat-hardenable molding composition comprising (1) a filler, (2) a heat-curable product of reaction of ingredients comprising (a) formaldehyde and (b) a monomeric amidogen compound containing not less than two amidogen groupings, each having two hydrogen atoms attached to the amidogen nitrogen atom, and ('3) at least one substance of the class consisting of polyethylene melamines, alcohol-reaction products of a polyethylene melamine and amine-reaction products of a polyethylene melamine, the ingredients of (2) and (3) being employed in a weight ratio of from 50 to per cent of the former to from 5 to 50 per cent of the latter, and the aforementioned polyethylene melamine being a polyamino-s-triazine wherein at least two of the amino nitrogen atoms each has one ethylene group attached thereto instead of the two hydrogen atoms.

16. An article of manufacture comprising the heat-hardened molding composition of claim 15. 17. A liquid composition comprising a solution containing (1) a soluble, thermosetting product of reaction of ingredients comprising (a) formaldehyde and (b) a monomeric amidogen compound containing not less than two amidogen groupings, each having two hydrogen atoms attached to the amidogen nitrogen atom, and (2) at least one substance of the class consisting of polyethylene melamines, alcohol-reaction products of a polyethylene melamine and amine-reaction products of a polyethylene melamine, the ingredients of (1) and (2) being employed in a weight ratio of from 50 to 95 per cent of the former to from 5 to 50 per cent of the latter, and the aforementioned polyethylene melamine being a polyamino-s-triazine wherein at least two of the amino nitrogen atoms each has one ethylene group attached thereto instead or the two hydrogen atoms.

18. A laminated article comprising superimposed sheets of fibrous material impregnated and bonded together with (1) a thermoset product of reaction of ingredients comprising (a) formaldehyde and (b) a. monomeric amidogen compound containing not less than two amidogeu groupings each having two hydrogen atoms attached to the amidogen nitrogen atom, and (2) at least one substance of the class consisting of polyethylene melamines, alcohol-reaction prod nets of a polyethylene melamine and amine-reaction products of a polyethylene melamine, the ingredienm of (1) and (2) being employed in a weight ratio of from 50 to 95 per cent of the former to from 5 to 50 per cent of the latter, and the aforementioned polyethylene melamine being a polyamino-s-triazine wherein at least REFERENCES CITED The following references are of record in the flle 01' this patent:

UNITED STATES PATENTS Name Date Dudley Oct. 3, 1950 Number 

1. A COMPOSITION OF MATTER COMPRISING (1) A PRODUCT OF REACTION OF INGREDIENTS COMPRISING (A) AN ALDEHYDE AND (B) A MONOMERIC AMIDOGEN COMPOUND CONTAINING NOT LESS THAN TWO AMIDOGEN GROUPINGS EACH HAVING AT LEAST ONE HYDROGEN ATOM ATTACHED TO THE AMIDOGEN NITROGEN ATOM, AND (2) AT LEAST ONE SUBSTANCE, OF THE CLASS CONSISTING OF POLYETHYLENE MELAMINES, ALCOHOL-REACTION PRODUCTS OF A POLYETHYLENE MELAMINE AND AMINE-REACTION PRODUCTS OF A POLYETHYLENE MELAMINE, THE INGREDIENTS OF (1) AND (2) BEING EMPLOYED IN A WEIGHT RATIO OF FROM 25 TO 97 PER CENT OF THE FORMER TO FROM 3 TO 75 PER CENT OF THE LATTER, AND THE AFOREMENTIONED POLYETHYLENE MELAMINE BEING A POLYAMINO-S-TRIAZINE WHEREIN AT LEAST TWO OF THE AMINO NITROGEN ATOMS EACH HAS ONE ETHYLENE GROUP ATTACHED THERETO INSTEAD OF THE TWO HYDROGEN ATOMS. 